TW201300433A - Functional polyurethane prepolymer, method of preparing polyurethane by using the same, and application method thereof - Google Patents

Abstract

This invention is a new and easy process for making functional polyurethane (PU) prepolymer by using a dicyclic carbonate oligomer (DCO) process via a microwave radiation process instead of conventional PU prepared by isocyanates as a raw material. The hazardous isocyanates are derived from toxic substance, phosgene. Then an amine-terminated polymer with a hydrophilic (ether) or a hydrophobic (polysiloxane) moiety is selected to react with DCO for ring-opening polymerization. This polymerization is accelerated drastically by microwave radiation and it results in a formation of PU prepolymer. Finally, acrylate-terminal groups are added and become UV-curable PU oligomer. It has been applied on textile surface coating after UV-radiation, it becomes long-lasting hydrophilic or hydrophobic textile surface treatment depending amino-terminated polymer is selected.

Description

Functional polyurethane prepolymer, method for preparing polyurethane using same and application method thereof

The invention relates to a functional polyurethane prepolymer, a method for preparing the polyurethane thereof and a application method thereof, in particular to a method for preparing a functional polyurethane prepolymer without using an isocyanate as a raw material, a method for preparing the polyurethane using the same, and an application method thereof.

Polyurethane (PU) is a commonly used polymer material, which is mostly used in sports cushioning materials, elastomer materials, adhesive materials and waterproof materials.

In the past, in the process of PU, mainly by using isocyanate (such as diisocyanate or polyisocyanate) and polyol (such as diol or hydroxyl functional polyol with high functionality) as the main material, but in this way In the process, it is often necessary to use Phosgene, which is highly polluting and highly toxic to the environment. If the phosgene is inadvertently leaked during the process, it will cause immediate health hazards such as pulmonary edema in the surrounding environment, resulting in immediate harm to the environment. The process itself is inherently dangerous, so scientists have tried to develop methods for making polyurethanes without using isocyanates as raw materials (Non-Isocyanates Routes).

In 1993, Takeshi Endo proposed to prepare PU in a method that does not use diisocyanate, which is reacted with a five-membered cyclic carbonate (Bis (cyclic carbonate)s) and a primary amine at room temperature to obtain a high yield. Β-position hydroxyl suspended PU (2-Hydroxyethylurethane), the reaction formula is as follows:

The starting of the hydroxy-suspended PU, the cyclic carbonate, is prepared as a typical nucleophilic ring opening reaction of ethylene oxide (Oxirane) and carbon dioxide. In the past literature, the cyclic carbonate was mainly composed of a ring. Oxygenethane and carbon dioxide are prepared by high pressure and catalyst reaction. Commonly used catalysts are amines (Amine), phosphine (Phosphine), quaternary amine salts, ruthenium compounds, porphyrins (Porpyrin) and transition metals. Things, such as process conditions and processes are more difficult. Until recently, the ring-opening reaction of ethylene oxide and carbon dioxide was developed under normal pressure (1 atm).

Professor Takeshi Endo et al. used a diamine and a dibasic carbonate to prepare a hydroxyl-suspended PU in a subsequent publication, and tested the relevant reaction conditions in a subsequent study on the ring-opening reaction of a cyclic carbonate. It is clearly pointed out that since this ring-opening reaction has high chemical selectivity and is not affected by the presence of water, alcohols and esters, the cyclic carbonate can be opened with a compound containing a primary amine under moderate reaction conditions. The polymerization reaction is shown in the following formula:

However, the foregoing method has also only developed a PU prepolymer having an amine functional group at the end, which has an average molecular weight of at most 5,000 to 8,000 g/mole, and cannot be effectively applied to the coating.

One aspect of the present invention is to provide a method for preparing a polyurethane prepolymer. The method of the present invention does not use a conventional isocyanate as a raw material, and does not require the use of phosgene in the process, but uses epoxy resin and carbon dioxide. As a main raw material, preparation of a polymer polyurethane prepolymer is carried out.

The steps of the preparation method of the invention include:

(1) Mixing: uniformly mixing an epoxy resin and a catalyst until the epoxy resin is completely dissolved to form a mixed raw material;

(2) Heating under reflux: carbon dioxide gas is introduced into the above-mentioned mixed raw material, and is continuously heated under reflux at a high temperature for a while to form a polyurethane prepolymer.

The aforementioned reaction steps can be expressed by the following equation:

Where R is

Another aspect of the present invention is to provide a method for preparing a polyurethane comprising the following steps:

(1) Mixing: mixing the epoxy resin and a first catalyst uniformly until the epoxy resin is completely dissolved to form a mixed raw material;

(2) heating and refluxing: introducing carbon dioxide gas into the aforementioned mixed raw material, and continuously heating at a high temperature for a period of time to form a polyurethane prepolymer;

(3) Microwave reaction: after the above-mentioned polyurethane prepolymer is uniformly mixed with a second catalyst, a ring-opening polymerization reaction is carried out to form a PU prepolymer having a terminal amine group;

(4) a Michael addition reaction; after uniformly mixing the aforementioned PU prepolymer with a third catalyst, a compound having an acrylic functional group is added at a low temperature to carry out a Michael addition reaction to form an ultraviolet Photohardenable polyurethane.

Another scope of the present invention is to provide a method for applying a polyurethane which is mainly composed of an epoxy resin, carbon dioxide and a polyamine compound, and includes the following steps:

(1) Immersion: uniformly mixing a polyurethane material and a photoinitiator to form a polyurethane raw material solution, and pressing a fabric into the polyurethane raw material solution for suction, and the fabric is fully absorbed, suspended, and allowed to stand. Waiting for the polyurethane raw material solution to evaporate in the atmosphere; and

(2) Photoreaction: The air-dried fabric was placed in a UV illuminator, and a medium-pressure mercury lamp was irradiated to the drying apparatus to fix the polyurethane raw material solution to the fabric.

The invention prepares a polyurethane prepolymer by using a method of preparing a polyisocyanate isocyanate and a polyhydric alcohol as a raw material, and preparing a polyurethane prepolymer by using an epoxy resin and carbon dioxide as a starting material, and the polyurethane prepolymer produced by the method The ultraviolet light crosslinkable polyurethane can be further synthesized and further coated on the surface of the fabric, and irradiated by ultraviolet light to form a water-repellent cross-linkable hydrophilic or hydrophobic PU fabric surface treatment.

In order to enable the reviewing committee to better understand the features of the present invention, the following detailed description is given by way of examples.

Embodiment 1

In this embodiment, Polypropylene glycol diglycidyl ether (hereinafter referred to as PPG-DGE) is used as a material to prepare a polyurethane prepolymer, and polyurethane (Polyurethane) is produced by using the aforementioned polyurethane prepolymer. Hereinafter, PU) and ultraviolet light crosslinkable polyurethane (UV-PU), and further, this ultraviolet light crosslinkable polyurethane (UV-PU) is used as a waterproof material.

(1) Preparation method of polyurethane prepolymer:

The polyurethane prepolymer formed in this embodiment is a PPG-type Cyclic Carbonate, and the epoxy resin diglycidyl ether (hereinafter referred to as PPG) used in the present embodiment. -DGE), the catalyst is lithium bromide (LiBr), which comprises the following steps: (S11) Mixing: PPG-DGE (5 moles) and lithium bromide (5 mole percentage) are uniformly mixed until PPG-DGE is completely dissolved, A mixed raw material is formed; and (S12) is heated and refluxed: carbon dioxide gas is introduced into the above-mentioned mixed raw material, and heating is continued under reflux at a pressure of atmospheric pressure at a temperature of 100 ° C for 24 hours to form a polycyclic carbonate product.

In this embodiment, the polycyclic carbonate product can be further washed with a large amount of deionized water and ethyl acetate to achieve the purpose of removing residual catalyst and purification, and a high purity polycyclic carbonate transparent colorless liquid can be obtained immediately.

Referring to Figures 1A and 1B, the disappearance state of the epoxy functional group (910 cm ^-1 ) and the formation state of the cyclic carbonate functional group (1800 cm ^-1 ) were observed by Fourier infrared spectrometer. The base is fully converted to a cyclic carbonate functional group.

(2) Preparation method of PU prepolymer containing terminal amine group:

The polycyclic carbonate product formed by the foregoing method can be further produced into a terminal prepolymer-containing PU prepolymer comprising the following steps: (S21) microwave treatment: taking the aforementioned polycyclic carbonate product (0.1 mol) Lithium bromide (5 mol%) and polyether diamine compound Jefferamine D-2000 (0.15 mol) were uniformly mixed, and then subjected to a ring reactor for half an hour by a microwave reactor having a power of 100 W to form a ring-opening polymerization reaction. A PU prepolymer having a terminal amine group.

Please refer to Fig. 2, which is a Fourier infrared spectrum of the PU obtained by the preparation method of the present PU. It can be seen from the figure that at the wavelength of 1720 cm ^-1 , the formation of the carbamate functional group is indeed present. It is obvious that in this step, the cyclic carbonate functional group (1800 cm ^-1 ) in the cyclic carbonic acid functional group disappears with the disappearance of the reaction time, and is converted into the urethane functional group. Generation of base (1720 cm ^-1 ).

Further, in this (S21) microwave treatment step, the polyether diamine compound (Jeffamine) is a polyamine compound, and those skilled in the art will know that, in practice, the compound can be a group of the following compounds. Group instead: 1,4-Butanediol bis-3-aminopropyl ether, Ethylene diamine, 1,12-Diaminododecane, aromatic diamine Class (m-Xylyene diamine) and hydrophobic polyether diamines (PDMS diamine).

In addition, in this (S21) microwave treatment step, it is also possible to selectively add a solvent for dilution to reduce the viscosity of the reactant. The solvent may be selected from ethyl lactate (EL), and the amount added in this embodiment is 10 ml, and the PU having a terminal amine group produced after the reaction, the Fourier infrared spectrum is also the same as that of the catalyst.

Moreover, the microwave intensity used in this (S21) microwave treatment can be adjusted between 50 and 150 W, and the microwave processing time is adjusted from 0.5 to 8 hours.

(3) UV-crosslinkable polyurethane (UV-PU):

The PU prepolymer formed by the foregoing method can be further produced into UV-PU, which comprises the following steps: (S31) 麦加加反应 reaction: the aforementioned PU prepolymer and the catalyst triethylamine (Triethyl amine) , abbreviated as TEA) (5 mole percentage) and after mixing evenly, add 20 ml of ethyl acetate, slowly add 0.2 mu of double acrylic functional diacrylate at 0 ° C (ice bath) The compound was subjected to a Michael addition reaction for 24 hours in this ice bath environment to remove the catalyst TEA and ethyl acetate to produce a UV-PU material.

In this (S31) methic acid addition reaction, it is also possible to participate in the reaction without adding an ethyl acetate solvent.

(4) Application of UV-PU:

The UV-PU material obtained by the method of the invention can form a network bond on the surface of the fabric, and can be smoothly embedded in the surface of the fiber bundle, so that the hydrophilic polymer in the fabric is not lost by washing, and the original can be retained. The hydrophilic property of the hydrophilic base resin is obtained as a long-acting water-resistant superabsorbent fabric, and the steps are as follows: immersion: the aforementioned UV-PU material is diluted to 1 to 10 wt% with ethyl acetate (EA). Concentration, and adding 5 phr of photoinitiator Benzoin alkyl ethe (1173) to form a UV-PU solution, and various different fabrics (PET) were placed in the above UV-PU solution. Pressing, after the fabric is fully absorbed, suspended and placed in the atmosphere to be evaporated and evaporated; and photoreaction: the air-dried superabsorbent fabric is placed in a UV illuminator and dried by a medium pressure mercury lamp. The device enables the double bond of the methyl ketone functional group in the UV-PU material to undergo a free radical crosslinking reaction and smoothly form a network bond, and can be smoothly embedded in the surface of the fiber bundle, so that the hydrophilicity in the fabric is high. Molecules will not be lost due to washing, but also Hydrophilic hydrophilic group to retain the original properties of the resin, the resulting fabric is the long-acting superabsorbent of washable.

Referring to Figure 3, the fabric coated with the UV-PU solution produced by the method of the present invention can be found by observing the woven fabric with a scanning electron microscope after 30 times of washing, and the UV-PU material is found on the surface of the fabric. The formed high-density network bond is not destroyed by the water washing factor, and still retains the hydrophilic character of the original hydrophilic-based resin.

In this embodiment, the photoinitiator may be substituted with a sensitizer (Benzophenone, BP for short) or a reactive diluent containing an acrylic double bond in a UV-PU solution. Ways to increase the concentration of acrylic double bonds in order to increase the crosslink density of the UV-PU material.

Embodiment 2

In this embodiment, a polyurethane prepolymer is prepared by using an epoxy resin bisphenol A type epoxy resin (DGEBA) as a material, and a polyurethane (Polyurethane) is produced by using the aforementioned polyurethane prepolymer. Hereinafter, PU) and ultraviolet light crosslinkable polyurethane (UV-PU), and further, this ultraviolet light crosslinkable polyurethane (UV-PU) is used as a waterproof material.

(1) Preparation method of polyurethane prepolymer:

The polyurethane prepolymer formed in this embodiment is a cyclic carbon carbonate (Bis), and the epoxy resin bisphenol A diglycidyl ether (DGEBA) used in the present embodiment. The catalyst is lithium bromide (LiBr), which comprises the following steps: (S11) Mixing: DGEBA (5 moles) and lithium bromide (5 mole percent) are uniformly mixed until DGEBA is completely dissolved to form a mixed raw material; (S12) Heating under reflux: Carbon dioxide gas was introduced into the above-mentioned mixed raw material, and heating was continued under reflux at a pressure of atmospheric pressure at a temperature of 100 ° C for 24 hours to form a BCC product.

The BCC product obtained in this embodiment can be further washed with a large amount of deionized water to remove residual catalyst and solvent, and to achieve the purpose of purification, followed by drying to obtain a fine white BCC powder.

Please refer to Figures 4A, 4B, 5, 6A and 6B. It can be seen from the figure that the disappearance state of the epoxy functional group (910 cm ^-1 ) and the cyclic carbonate functional group (1800 cm ^-1 ) were detected by Fourier infrared spectrometer. In the state of formation, it is apparent that the epoxy functional group is sufficiently converted into a cyclic carbonic acid functional group; moreover, the molecular structure of the BCC product produced after the step of the present embodiment can be confirmed by further structural analysis by nuclear magnetic resonance.

(2) Preparation method of PU prepolymer containing terminal amine group:

The BBC product formed by the foregoing method can be further produced into a PU prepolymer comprising the following steps: (S21) microwave treatment: taking the aforementioned BBC product (0.1 mol), lithium bromide (5 mol percentage) and fat The amine amine Jefferamine D-2000 (0.15 mole) was uniformly mixed and then subjected to a ring-opening polymerization reaction using a microwave reactor having a power of 100 W for half an hour to form a PU prepolymer having a terminal amine group.

Please refer to Figure 7 for the Fourier infrared spectrum of the PU obtained by this method. It can be seen from the figure that at the wavelength of 1720 cm ^-1 , the presence of the carbamate functional group is indeed formed. In this step, the cyclic carbonate functional group (1800 cm ^-1 ) in the cyclic carbonic acid functional group disappears with the disappearance of the reaction time, and is converted into a carbamate functional group ( The formation of 1720 cm ^-1 ), and the PU prepolymer formed by this method can have a molecular weight of up to 20,000 or more, which will be easier for subsequent applications.

In this (S21) microwave treatment step, a solvent may also be added to achieve the effect of diluting and reducing the viscosity of the reactant. The solvent may be selected from ethyl lactate (EL) or ethyl acetate (EA). In the example, the amount of addition is 10 ml, and the PU prepolymer having a terminal amine group produced after the reaction has the same Fourier infrared spectrum as the catalyst.

(3) UV-crosslinkable polyurethane (UV-PU):

The PU prepolymer formed by the foregoing method can be further produced into UV-PU, which comprises the following steps: (S31) 麦加加反应 reaction: the aforementioned PU prepolymer and the catalyst triethylamine (Triethyl amine) , abbreviated as TEA) (5 mole percentage) and after mixing evenly, add 20 ml of ethyl acetate, slowly add 0.2 mu of double acrylic functional group (diacrylate) at 0 ° C (ice bath) The compound was subjected to a Michael addition reaction for 24 hours in this ice bath environment to remove the catalyst TEA and ethyl acetate to produce a UV-PU material.

In this (S31) methic acid addition reaction, it is also possible to participate in the reaction without adding an ethyl acetate solvent.

In one embodiment, the compound having a double acryl functional group is 3-Acryloyloxy-2-hydroxypropyl methacrylate.

(4) Application of UV-PU:

The UV-PU material obtained by the method of the invention can form a network bond on the surface of the fabric, and can be smoothly embedded in the surface of the fiber bundle, so that the hydrophilic polymer in the fabric is not lost by washing, and the original can be retained. The hydrophilic property of the hydrophilic base resin is obtained as a long-acting water-resistant superabsorbent fabric, and the steps are as follows: immersion: the aforementioned UV-PU material is diluted to 1 to 10 wt% with ethyl acetate (EA). Concentration, and adding 5 phr of photoinitiator (Benzoin alkyl ethe, abbreviated as 1173) to form a UV-PU solution, put a variety of different fabrics (PET) into the above UV-PU solution for pressure, until the fabric is sufficient After absorption, it is suspended and placed in the atmosphere to be evaporated and evaporated; and photoreaction: the air-dried superabsorbent fabric is placed in a UV illuminator, and the UV-PU material is irradiated by a medium pressure mercury lamp. The double bond of the methyl ketone functional group can undergo a radical crosslinking reaction and smoothly form a network bond, and can be smoothly embedded in the surface of the fiber bundle, so that the hydrophilic polymer in the fabric is not washed by water. Loss, you can still retain the original The hydrophilic properties of water-based resin, the resulting fabric is the long-acting superabsorbent of washable.

Referring to Figure 8, the fabric coated with the UV-PU solution produced by the method of the present invention can be found by observing the woven fabric with a scanning electron microscope after 30 times of washing, and the UV-PU material is found on the surface of the fabric. The formed high-density network bond is not destroyed by the water washing factor, and still retains the hydrophilic character of the original hydrophilic-based resin.

In this embodiment, the photoinitiator may be substituted with a sensitizer (Benzophenone, BP for short) or a reactive diluent containing an acrylic double bond in a UV-PU solution. Instead of way to increase the crosslink density of UV-PU materials.

In the foregoing examples, the epoxy resin selected is a bisphenol A type epoxy resin or a bisphenol A diglycidyl ether (DGEBA), but when it is actually implemented, it should not be limited to other types of epoxy trees. Esters, for example: Epoxy-128, Epoxy-506, Epoxy-904, aliphatic epoxy, polypropylene glycol diglycidyl ether PPG-DGE), polyethylene glycol diglycidyl ether (PEG-DGE), and mixtures of the foregoing may be used as the starting materials for the present invention.

In summary, the present invention provides a process different from the conventional polyurethane prepolymer and ultraviolet curing polyurethane, which can eliminate the harmful effects of using phosgene without using isocyanate and polyol as raw materials. The material needs and reduces the harm to the environment. In addition, the method of the invention is simple in operation and has no special environmental conditions, and is more environmentally friendly and energy-saving and carbon-reducing than the conventional preparation method. The advantages of the effect.

Fig. 1A is a Fourier infrared spectrum of polypropylene diglycidyl used in Example 1.

Fig. 1B is a Fourier infrared spectrum of the PPG-type Cyclic Carbonates formed in Example 1.

Fig. 2 is a Fourier infrared spectrum of the polyurethane (PU) formed in Example 1.

Fig. 3 is a photograph of the woven fabric fiber observed by a scanning electron microscope after the ultraviolet light crosslinkable polyurethane formed in Example 1 was applied to the surface of the fabric and washed with water for 30 times.

Fig. 4A is a Fourier infrared spectrum of the bisphenol A type epoxy resin used in the second embodiment.

Figure 4B is a Fourier infrared spectrum of the polycyclic carbonate (BCC) formed in Example 2.

Fig. 5 is a ¹ H nuclear magnetic resonance spectrum of a bisphenol A type epoxy resin used in Example 2.

Figure 6A is a ¹ H NMR spectrum of the polycyclic carbonate (BCC) formed in Example 2.

Figure 6B is a ¹³ C nuclear magnetic resonance spectrum of the polycyclic carbonate (BCC) formed in Example 2.

Figure 7 is a Fourier infrared spectrum of the polyurethane (PU) formed in Example 2.

Claims (33)

A method for preparing a polyurethane prepolymer, which comprises a mono-epoxy resin and carbon dioxide as a main raw material, comprising the following steps: mixing: mixing the epoxy resin and a catalyst uniformly until the epoxy resin is completely dissolved To form a mixed raw material; and heating under reflux: introducing carbon dioxide gas into the mixed raw material, and continuing to reflux at a high temperature for a while to form a polyurethane prepolymer. The preparation method according to claim 1, wherein the epoxy resin is selected from the group consisting of bisphenol A type epoxy resin (DGEBA), bisphenol A diglycidyl ether Epoxy-128, Epoxy-506, Epoxy-904, Epoxy-904, aliphatic epoxy, polypropylene glycol diglycidyl ether (PPG-DGE) ), polyethylene glycol diglycidyl ether (PEG-DGE) and a mixture of the foregoing compounds. The preparation method according to claim 2, wherein the catalyst is lithium bromide. The preparation method according to claim 2, wherein the high temperature is 100 °C. The preparation method of claim 2, wherein the heating time is 12 to 24 hours. The preparation method according to claim 1, wherein a solvent is further added to the mixing step. The preparation method according to any one of claims 1 to 6, wherein the heating and refluxing step further comprises the following steps to produce a terminal amino group-containing polyurethane prepolymer: microwave treatment: taking the The polyesteramine prepolymer is uniformly mixed with a catalyst and a polyamine compound, and then subjected to a ring-opening polymerization reaction for a period of time by a microwave reactor to form the polyurethane ester prepolymer having a terminal amine group. The preparation method of claim 7, wherein a further dilution solvent is added to the microwave treatment step. The preparation method according to claim 8, wherein the dilution solvent is ethyl acetate or ethyl lactate. The preparation method according to claim 7, wherein the catalyst of the microwave treatment step is lithium bromide. The preparation method according to claim 7, wherein the microwave reactor has a working time of 0.5 to 8 hours. The preparation method according to claim 7, wherein the microwave reactor has a microwave power of 50 to 150 W. The preparation method according to claim 7, wherein the polyamine compound is selected from the group consisting of polyether diamines (Jeffamine) and hydrophilic aliphatic diamines (1, 4). -Butanediol bis-3-aminopropyl ether), Ethylene diamine, 1,12-Diaminododecane, m-Xylyene diamine and hydrophobic polyether diamine Compound (PDMS diamine). A method for preparing a polyurethane is mainly composed of an epoxy resin, carbon dioxide and a polyamine compound, which comprises the following steps: mixing: mixing an epoxy resin and a catalyst to the epoxy tree The ester is completely dissolved to form a mixed raw material; heated to reflux: carbon dioxide gas is introduced into the mixed raw material, and is continuously heated under reflux at a high temperature for a period of time to form a polyurethane prepolymer; microwave treatment: taking the polyester amine prepolymer After uniformly mixing with a catalyst and a polyamine compound, a microwave reactor is used for a period of time to carry out a ring-opening polymerization reaction to form the polyurethane ester prepolymer having a terminal amine group; and a Michael addition reaction: After the terminal amine-based polyurethane prepolymer is uniformly mixed with a catalyst, a compound having a double acrylic resin is slowly dropped into a low temperature environment, and the wheat is continuously subjected to the low temperature environment. The reaction is carried out to obtain an ultraviolet light crosslinkable polyurethane. The preparation method according to claim 14, wherein the epoxy resin is selected from the group consisting of bisphenol A type epoxy resin (DGEBA), bisphenol A diglycidyl ether Epoxy-128, Epoxy-506, Epoxy-904, Epoxy-904, aliphatic epoxy, polypropylene glycol diglycidyl ether (PPG-DGE) ), polyethylene glycol diglycidyl ether (PEG-DGE) and a mixture of the foregoing compounds. The preparation method according to claim 14, wherein the catalyst of the mixing step is lithium bromide. The preparation method according to claim 14, wherein the high temperature is 100 °C. The preparation method according to claim 14, wherein the heating time is 12 to 24 hours. The preparation method of claim 14, wherein a solvent is further added to the mixing step. The preparation method of claim 14, wherein a further dilution solvent is added to the microwave treatment step. The preparation method according to claim 20, wherein the dilution solvent is ethyl acetate or ethyl lactate. The preparation method according to claim 14, wherein the catalyst of the microwave treatment step is lithium bromide. The preparation method according to claim 14, wherein the microwave reactor has a working time of 0.5 to 8 hours. The preparation method of claim 14, wherein the microwave reactor has a microwave power of 50 to 150 W. The preparation method according to claim 14, wherein the low temperature of the 麦加加反应 reaction is 0 °C. The preparation method according to claim 14, wherein the polyamine compound is selected from the group consisting of polyether diamines (Jeffamine) and hydrophilic aliphatic diamines (1, 4). -Butanediol bis-3-aminopropyl ether), Ethylene diamine, 1,12-Diaminododecane, m-Xylyene diamine and hydrophobic polyether diamine Compound (PDMS diamine). The preparation method according to claim 14, wherein the compound having a double acrylate functional group is 3-acryloyl-2-hydroxypropylmethyl acrylate (3-Acryloyloxy-2). -hydroxypropyl methacrylate). The preparation method according to claim 14, wherein the microwave treatment or the wheat addition reaction is added with a diluent solvent. The preparation method according to claim 28, wherein the dilution solvent is ethyl acetate. A method for applying a polyurethane, the polyamine ester is mainly composed of an epoxy resin, carbon dioxide and a polyamine compound, and the application method comprises the following steps: immersing: uniformly mixing a polyurethane material and a photoinitiator Mixing to form a polyurethane raw material solution, putting a fabric into the polyurethane raw material solution for pressure suction, allowing the fabric to be fully absorbed, suspended and resting in the atmosphere to evaporate the polyurethane raw material solution; and photoreaction: The air-dried fabric is placed in a UV illuminator, and the polyurethane equipment is fixed to the fabric by irradiating the drying apparatus with a medium pressure mercury lamp. The application method according to claim 30, wherein the method for producing the polyurethane comprises the following steps: mixing: mixing an epoxy resin and a catalyst until the epoxy resin is completely dissolved to form a Mixing raw materials; heating and refluxing: introducing carbon dioxide gas into the mixed raw material, and continuing to reflux for a period of time at a high temperature to form a polyurethane prepolymer; microwave treatment: taking the polyesteramine prepolymer and a catalyst and a plurality of After the amine compound is uniformly mixed, it is subjected to a microwave reactor for a period of time to carry out a ring-opening polymerization reaction to form the polyurethane ester prepolymer having a terminal amine group; and a Michael addition reaction: the polyurethane ester prepolymer and the After the catalyst is uniformly mixed, a compound having a double acrylic acid diacrylate is slowly dropped into a low temperature environment, and the wheat addition reaction is continued in the low temperature environment to obtain an ultraviolet light crosslinkable. Type polyurethane material. The method of application of claim 31, wherein the fabric is a Polyethylene Terephthalate (PET) fabric. The method of application of claim 32, wherein the photoinitiator is Benzoin alkyl ethe.